# Patent

## Title
Color liquid crystal display device comprising a red filter segment having a red pigment combination wherein the weight ratio of an azo-based red pigment and an anthraquinone-based red pigment ranges from 20/80 to 80/20

## Abstract

A color liquid crystal display device includes a liquid crystal display element and a backlight unit. The liquid crystal display element includes a color filter having a red filter segment, a green filter segment, and a blue filter segment. The red filter segment is prepared from a red photosensitive resin composition which includes a pigment combination, an alkali-soluble resin, a compound having an ethylenic group, and a photoinitiator. The pigment combination includes an azo-based red pigment and an anthraquinone-based red pigment. A weight ratio of the azo-based red pigment to the anthraquinone-based red pigment ranges from 20/80 to 80/20. The backlight unit is coupled to the liquid crystal display element and has a color temperature ranging from 6,000 K to 20,000 K.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority of Taiwanese Application No. 099130036, filed Sep. 6, 2010.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a color liquid crystal display device, more particularly to a color liquid crystal display device having high brightness and high contrast.
2. Description of the Related Art
Recently, liquid crystal display devices have been increasingly developed due to their characteristics, such as light weight, thin profile, and power saving.
It is desirable to provide a liquid crystal display device having high brightness and high contrast.
JP 10-148712 discloses a color resist composition for a color filter of a liquid crystal display device. An anthraquinone-based red pigment such as C.I. Pigment Red 177 is used in a red pixel of the color filter. The red pigment is mechanically micronized to improve the dispersion thereof, such that the contrast of a liquid crystal display device can be increased thereby. However, the brightness of the color filter can not be effectively enhanced due to the spectral properties of the red pigment. Moreover, in JP 10-148712, an azo-based red pigment such as C.I. Pigment Red 166 is mixed with C.I. Pigment Red 177 and yellow pigments so as to improve color characteristics. Although the color reproduction area of the color filter is expanded, the contrast can not be enhanced.
In JP 11-231516 and JP 2002-328217, C.I. Pigment Red 254, a diketo-pyrrolopyrrole-based red pigment, is used. Compared to C.I. Pigment red 177, the transmission spectrum at about 600 nm of C.I. Pigment Red 254 shifts toward shorter wavelength, and the red absorption of the backlight is reduced so as to enhance the brightness. However, the cohesion among the micronized particles of C.I. Pigment Red 254 is too strong. Therefore, it is difficult to disperse the micronized particles of C.I. Pigment Red 254, such that the contrast can not be enhanced.
Therefore, it is still required in the art to provide a color liquid crystal display device having both high brightness and high contrast.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a color liquid crystal display device having high brightness and high contrast.
The color liquid crystal display device according to this invention includes a liquid crystal display element and a backlight unit. The liquid crystal display element includes a color filter having a red filter segment, a green filter segment, and a blue filter segment. The red filter segment is prepared from a red photosensitive resin composition which includes a pigment combination, an alkali-soluble resin, a compound having an ethylenic group, and a photoinitiator. The pigment combination includes an azo-based red pigment and an anthraquinone-based red pigment. A weight ratio of the azo-based red pigment to the anthraquinone-based red pigment ranges from 20/80 to 80/20. The backlight unit is coupled to the liquid crystal display element and has a color temperature ranging from 6,000 K to 20,000 K.



BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become apparent in the following detailed description of the preferred embodiments with reference to the accompanying drawings, of which:
FIG. 1 is a fragmentary schematic view of a preferred embodiment of a color liquid crystal display device according to this invention; and
FIG. 2 is a sectional view of a white light emitting diode used in the preferred embodiment.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, the preferred embodiment of the color liquid crystal display device according to this invention includes a liquid crystal display element 10 and a backlight unit 20.
The liquid crystal display element 10 includes a first substrate 13, a second substrate 14 spaced apart from the first substrate 13, a color filter 11 coupled to the first substrate 13, two alignment layers 15 respectively disposed on the color filter 11 and the second substrate 14 and facing toward each other, liquid crystal 12 disposed between the alignment layers 15, and two polarizers 16 respectively coupled to the first and second substrates 13, 14 and distal from the liquid crystal 12. The first substrate 13 is a color filter side substrate, and the second substrate 14 is a thin film transistor side substrate. Since the method for manufacturing the liquid crystal display element 10 is well known in the art, it is not described in detail herein.
The color filter 11 has at least one red filter segment, at least one green filter segment, and at least one blue filter segment. The red filter segment is made of a red photosensitive resin composition which includes (A) a pigment combination, (B) an alkali-soluble resin, (C) a compound having an ethylenic group, (D) a photoinitiator, and (E) an organic solvent. The pigment combination includes (A-1) an azo-based red pigment and (A-2) an anthraquinone-based red pigment. A weight ratio of the azo-based red pigment to the anthraquinone-based red pigment ranges from 20/80 to 80/20.
The pigment combination is used in an amount ranging generally from 100 to 800 parts by weight, preferably from 150 to 600 parts by weight, and more preferably from 200 to 500 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
Specifically, the azo-based red pigment is used in an amount ranging generally from 20 to 250 parts by weight, preferably from 40 to 200 parts by weight, and more preferably from 60 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin. The anthraquinone-based red pigment is used in an amount ranging generally from 20 to 250 parts by weight, preferably from 40 to 200 parts by weight, and more preferably from 60 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
As described above, the weight ratio of the azo-based red pigment to the anthraquinone-based red pigment ranges from 20/80 to 80/20. When the weight ratio of the azo-based red pigment to the anthraquinone-based red pigment is less than 20/80, the contrast of the color liquid crystal display device can not be enhanced. When the weight ratio of the azo-based red pigment to the anthraquinone-based red pigment is more than 80/20, the brightness of the color liquid crystal display device may be reduced. Preferably, the weight ratio of the azo-based red pigment to the anthraquinone-based red pigment ranges from 30/70 to 80/20. More preferably, the weight ratio of the azo-based red pigment to the anthraquinone-based red pigment ranges from 40/60 to 80/20.
Preferably, examples of the azo-based red pigment include, but are not limited to, C.I. Pigment Red 144, C.I. Pigment Red 166, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 242, C.I. Pigment Red 248, C.I. Pigment Red 262, and combinations thereof. Examples of the anthraquinone-based red pigment include, but are not limited to, C.I. Pigment Red 83, C.I. Pigment Red 89, P.I. Pigment Red 177, and combinations thereof. More preferably, the azo-based red pigment is C.I. Pigment Red 166, P.I. Pigment Red 242, or a combination thereof. The anthraquinone-based red pigment is C.I. Pigment Red 89, C.I. Pigment Red 177, or a combination thereof.
The mean particle size of the primary particles of the azo-based red pigment and the anthraquinone-based red pigment ranges generally from 10 to 200 nm, preferably from 20 to 150 nm, and more preferably from 30 to 100 nm.
The micronization of the mean particle size of the primary particles of the azo-based red pigment and the anthraquinone-based red pigment can be conducted by a grinding method in which the pigments are mechanically ground, a precipitation method in which the pigments are dissolved in a good solvent and then are precipitated using a poor solvent, or a synthetic precipitation in which the pigments of finer particle size are produced in the synthesis process of the pigments.
The pigment combination can be used in combination with a dispersant, if necessary. Examples of the dispersant include, but are not limited to, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone-based surfactants, and fluorine-based surfactants. Examples of the surfactants include polyethylene oxide alkyl ethers, such as polyethylene oxide dodecyl ether, polyethylene oxide stearoyl ether, polyethylene oxide oleyl ether, or the like; polyethylene oxide alkyl phenyl ethers, such as polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, or the like; polyethylene glycol diesters, such as polyethylene glycol dilaurate, polyethylene glycol distearate, or the like; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; or the like. Examples of the commercial surfactants include KP manufactured by Shin-Etsu Chemical Col, Ltd., SF-8427 manufactured by Toray Dow Corning Silicon, Polyflow manufactured by Kyoeisha Chemical Co., Ltd., F-Top manufactured by Tochem Products Co., Ltd., Megafac manufactured by Dainippon Ink and Chemicals, Incorporated, Fluorade manufactured by Sumitomo 3M, Asahi Guard and Surflon both manufactured by Asahi Glass, or the like. The above examples of the surfactant can be used alone or in combinations thereof.
An additional red pigment and/or a yellow pigment can be added into the pigment combination so as to adjust the chromaticity of the pigment combination. Examples of the additional red pigment include, but are not limited to, quinacridones, perylenes, pyranthrene-8,16-diones, and combinations thereof. Examples of the yellow pigment include, but are not limited to, isoindoles, quinaphthalones, anthraquinones, and combinations thereof. Preferably, the yellow pigment is selected from quinaphthalones. More preferably, the yellow pigment is selected from C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 10, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 97, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 128, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 167, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Pigment Yellow 219, or the like. These yellow pigments can be used alone or in combinations thereof. The yellow pigment is preferably selected from C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Yellow 219, and combinations thereof in consideration of color purity and transparency.
The additional red pigment is used in an amount ranging generally from 5 to 100 parts by weight, preferably from 10 to 80 parts by weight, and more preferably from 15 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin. The yellow pigment is used in an amount ranging generally from 5 to 100 parts by weight, preferably from 10 to 80 parts by weight, and more preferably from 15 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
The alkali-soluble resin is obtained by subjecting an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer to conduct a copolymerization. Preferably, the amounts of the ethylenically unsaturated monomer having one or more carboxyl groups and the another copolymerizable ethylenically unsaturated monomer used in the copolymerization reaction are 50-95 parts by weight and 5-50 parts by weight, respectively, based on 100 parts by weight of the sum of the ethylenically unsaturated monomer having one or more carboxyl groups and the another copolymerizable ethylenically unsaturated monomer.
Examples of the aforementioned ethylenically unsaturated monomer having one or more carboxyl groups include, but are not limited to, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acryloylethoxy succinate, 2-methacryloylethoxy succinate, or the like; unsaturated dicarboxylic acids and/or anhydrides thereof, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, or the like; and unsaturated polycarboxylic acids having at least three carboxyl groups in the molecules and/or anhydrides thereof; or the like. Preferably, the ethylenically unsaturated monomer having one or more carboxyl groups is selected from acrylic acid, methacrylic acid, 2-acryloylethoxy succinate, and 2-methacryloylethoxy succinate. More preferably, the ethylenically unsaturated monomer having one or more carboxyl groups is selected from 2-acryloylethoxy succinate and 2-methacryloylethoxy succinate. The ethylenically unsaturated monomer having one or more carboxyl groups is used for increasing the pigment dispersion, enhancing the development speed, and reducing the residue.
Examples of the another copolymerizable ethylenically unsaturated monomer include, but are not limited to, vinyl aromatic compounds, such as styrene, α-methyl styrene, o-vinyl toluene, p-chlorostyrene, methoxystyrene, or the like; maleimides, such as N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-cyclohexylmaleimide, or the like; unsaturated carboxylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, docosyl methacrylate, dicyclopentenyloxyethyl acrylate, or the like; unsaturated amino alkyl carboxylates, such as N,N-dimethyl aminoethyl acrylate, N,N-dimethyl aminoethyl methacrylate, N,N-diethyl aminopropyl acrylate, N,N-dimethyl aminopropyl methacrylate, N,N-dibutyl aminopropyl acrylate, or the like; unsaturated glycidyl carboxylates, such as glycidyl acrylate, glycidyl methacrylate, or the like; vinyl carboxylates, such as vinyl acetate, vinyl propionate, vinyl butyrate, or the like; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether, or the like; vinyl cyanides, such as acrylonitrile, methyl acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, or the like; unsaturated amides, such as acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, or the like; and aliphatic conjugate dienes, such as 1,3-butadiene, iso-propylene, chloroprene, or the like.
Preferably, the another copolymerizable ethylenically unsaturated monomer is selected from styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and dicyclopentenyloxyethyl acrylate.
Examples of the solvent suitable for preparing the alkali-soluble resin include, but are not limited to, (poly)alkylene glycol monoalkyl ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, or the like; (poly)alkylene glycol monoalkyl ether acetates, such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, or the like; other ethers, such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, or the like; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, or the like; alkyl lactate, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, or the like; other esters, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, n-amyl acetate, iso-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, iso-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, or the like; aromatic hydrocarbons, such as toluene, xylene, or the like; and carboxylic acid amide, such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or the like. Preferably, the solvent is selected from propylene glycol methyl ether acetate and ethyl 3-ethoxypropionate. The aforesaid examples of the solvent can be used alone or in admixture of two or more thereof.
The initiator used for preparing the alkali-soluble resin is a free radical polymerization initiator, examples of which include, but are not limited to, azo compounds, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis-2-methylbutyronitrile, or the like; and peroxides, such as benzoyl peroxide, or the like.
The compound having an ethylenic group used in the present invention is a compound having one or more ethylenically unsaturated groups.
Examples of the compound having one ethylenically unsaturated group include, but are not limited to, acrylamide,(meth)acryloylmorpholine, 7-amino-3,7-dimethyloctyl(meth)acrylate, iso-butoxymethyl(meth)acrylamide, iso-bornyloxyethyl(meth)acrylate, iso-bornyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, ethyl diethylene glycol(meth)acrylate, t-octyl(meth)acrylamide, diacetone(meth)acrylamide, dimethylaminoethyl(meth)acrylate, dodecyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, dicyclopentenyl(meth)acrylate, N,N-dimethyl(meth)acrylamide, tetrachlorophenyl(meth)acrylate, 2-tetrachlorophenoxy ethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, tetrabromophenyl(meth)acrylate, 2-tetrabromophenoxyethyl(meth)acrylate, 2-trichlorophenoxyethyl(meth)acrylate, tribromophenyl(meth)acrylate, 2-tribromophenoxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl(meth)acrylate, pentachlorophenyl(meth)acrylate, pentabromophenyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, bornyl(meth)acrylate, or like.
Examples of the compound having two or more ethylenically unsaturated groups include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tri(2-hydroxyethyl) isocyanate di(meth)acrylate, tri(2-hydroxyethyl) isocyanate tri(meth)acrylate, caprolactone-modified tri(2-hydroxyethyl) isocyanate tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate, ethylene oxide (hereinafter abbreviated as EO) modified trimethylolpropyl tri(meth)acrylate, propylene oxide (hereinafter abbreviated as PO) modified trimethylolpropyl tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neo-pentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ditrimethylolpropyl tetra(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, EO-modified hydrogenated bisphenol A di(meth)acrylate, PO-modified hydrogenated bisphenol A di(meth)acrylate, PO-modified glycerol triacrylate, EO-modified bisphenol F di(meth)acrylate, phenol novolac polyglycidyl ether(meth)acrylate, or the like.
Preferably, the compound having an ethylenic group is selected from trimethylolpropyl triacrylate, EO-modified trimethylolpropyl triacrylate, PO-modified trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropyl tetraacrylate, and PO-modified glycerol triacrylate. The aforesaid examples of the compound having an ethylenic group can be used alone or in admixture of two or more thereof.
The compound having an ethylenic group is used in an amount ranging generally from 10 to 500 parts by weight, preferably from 30 to 400 parts by weight, and more preferably from 50 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
The photoinitiator suitable for the present invention is selected from O-acyloxime compounds, triazine compounds, acetophenone compounds, biimidazole compounds, or benzophenone compounds. The photoinitiator is used in an amount ranging generally from 2 to 200 parts by weight, preferably from 5 to 180 parts by weight, and more preferably from 10 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
Examples of the O-acyloxime compounds include, but are not limited to, 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime), 1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethylketo 1-(O-acetyloxime), 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-ethylketo 1-(O-acetyloxime), 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-ethylketo 1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-4-tetrapyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-5-tetrafurylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-5-tetrapyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-4-tetrafurylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-4-tetrapyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-5-tetrafurylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-5-tetrapyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)benzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acety loxime), or the like.
Examples of the triazine compounds include, but are not limited to, 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine, 2-trichloromethyl-4-amino-6-(p-methoxy)styryl-s-triazine, or the like.
Examples of the acetophenone compounds include, but are not limited to, p-dimethylaminoacetophenone, α,α′-dimethoxyazoxyacetophenone, 2,2′-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propan one, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, or the like.
Examples of the biimidazole compounds include, but are not limited to, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-fluorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-methylphenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-methoxyphenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(o-ethylphenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(p-methoxyphenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,2′,4,4′-tetramethoxyphenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, or the like.
Examples of the benzophenone compounds include, but are not limited to, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, or the like.
Preferably, the photoinitiator is selected from 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethylketo 1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethylketo-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, and 4,4′-bis(diethylamino)benzophenone.
In addition to the aforesaid photoinitiators, other initiators can be further added into the red photosensitive resin composition of the present invention. Examples of the other initiators include, but are not limited to, α-diketone compounds, such as benzil, acetyl, or the like; acyloin compounds, such as benzoin, or the like; acyloin ether compounds, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or the like; acylphosphine oxide compounds, such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethyl benzyl phosphine oxide, or the like; quinone compounds, such as anthraquinone, 1,4-naphthoquinone, or the like; halide compounds, such as phenacyl chloride, tribromomethyl phenylsulfone, tris(trichloromethyl)-s-triazine, or the like; and peroxide compounds, such as di-tert-butyl peroxide; or the like.
All the above components except the pigment combination are generally dissolved in an appropriate organic solvent to prepare a liquid composition, and the pigment combination is then mixed with the liquid composition to prepare the red photosensitive resin composition. Any solvents, which are inert to and can disperse or dissolve the alkali-soluble resin, the compound having an ethylenic group, and the photoinitiator and which have appropriate volatility, can be used.
The organic solvent for preparing the red photosensitive resin composition is used in an amount ranging generally from 500 to 5,000 parts by weight, preferably from 800 to 4,500 parts by weight, and more preferably from 1,000 to 4,000 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
The organic solvent suitable for preparing the red photosensitive resin composition can be selected from the examples of the solvent for preparing the alkali-soluble resin. Preferably, the organic solvent suitable for preparing the red photosensitive resin composition is propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate. The examples of the organic solvent suitable for preparing the red photosensitive resin composition can be used alone or in combinations thereof.
The red photosensitive resin composition in the present invention can contain other additives, such as fillers, polymers other than the alkali-soluble resin, adhesion agents, antioxidants, UV absorbents, anti-coagulants, or the like according to the specific requirements for the physical and/or chemical properties of the red filter segment made from the red photosensitive resin composition.
Examples of the fillers include glass, alumina, or the like. Examples of the polymers other than the alkali-soluble resin include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoro alkyl acrylate, or the like. Examples of the adhesion agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryl oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or the like. Examples of the antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, or the like. Examples of the UV absorbents include 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, or the like. Examples of the anti-coagulants include sodium polyacrylate, or the like.
The other additives are used in an amount ranging generally from 0 to 10 parts by weight, preferably from 0 to 6 parts by weight, and more preferably from 0 to 3 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
The green filter segment and the blue filter segment in the present invention can be made of a conventional green photosensitive resin composition and a conventional blue photosensitive resin composition, respectively. The components of the green and blue photosensitive resin compositions are substantially identical to those of the red photosensitive resin composition except that instead of the pigment combination used in the red photosensitive resin composition, a green pigment is used in the green photosensitive resin composition whereas a blue pigment is used in the blue photosensitive resin composition. Examples of the green pigment include, but are not limited to, C.I. Pigment Green 07, 36, 37, 58, alone or in combinations thereof, combined with C.I. Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 55, 83, 93, 109, 110, 128, 138, 139, 150, 153, 154, 155, 166, 168, 180, 185, 211, 219, alone or in combinations thereof. Preferably, the green pigment includes, but it not limited to, C.I. Pigment Green 07, 36, 58, alone or in combinations thereof, with C.I. Pigment Yellow 13, 138, 139, 150, alone or in combinations thereof. Examples of the blue pigment include, but are not limited to, C.I. Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 21, 22, 60, 64, alone or in combinations thereof, combined with C.I. Pigment Purple 19, 23, 29, 32, 33, 36, 37, 38, 40, 50, alone or in combinations thereof. Preferably, the blue pigment is C.I. Pigment Blue 15:6 combined with C.I. Pigment Purple 23. In the following illustrative examples, the green pigment is C.I. Pigment Green 58 combined with C.I. Pigment Yellow 150, and the blue pigment is C.I. Pigment Blue 15 combined with C.I. Pigment Purple 23.
The red photosensitive resin composition in a liquid state for the color filter in the present invention can be formed by blending the alkali-soluble resin, the compound having an ethylenic group, and the photoinitiator with the pigment combination in the organic solvent using a mixer. The red photosensitive resin composition is coated on a substrate by a spin coating method, a knife coating method, an ink-jet coating method, a roller coating method, or the like, and is then dried under reduced pressure to remove most of the solvent. After completely evaporating the residual solvent by pre-baking, a coating film is formed. Operation conditions for the drying under reduced pressure and the pre-baking depend on kinds and amounts of the components used in the red photosensitive resin composition. In general, the drying under reduced pressure is carried out at a pressure from 0 to 200 mm Hg for a period from 1 to 60 seconds. The pre-baking is carried out at a temperature from 70° C. to 110° C. for a period from 1 to 15 minutes. The coating film is then exposed to UV light through a specific photo mask, and is developed in a developer solution at a temperature of 23±2° C. for a period from 15 seconds to 5 minutes to dissolve and remove the unexposed portions of the coating film so as to obtain a desired pattern. The substrate with the desired pattern of the coating film is washed with water, is dried with compressed air or compressed nitrogen, and is heated at a temperature from 100 to 280° C. for a period of 1 to 15 minutes in a heating device, such as a hot plate or an oven so as to remove evaporative components and to subject the unreacted ethylenic compound contained in the coating film to conduct a heat curing reaction. The red filter segment can be obtained thereby. The green and blue filter segments can be obtained using the green and blue photosensitive resin compositions, respectively, following the procedure for making the red filter segment. A color filter can be obtained thereby.
The UV light used for the exposure of the coating film can be g line, h line, i line, or the like. The UV lamp for providing the UV light is a (ultra)high-pressure mercury lamp or a metal halide lamp. The substrate used to form the color filter is made from bare glass, soda glass, Pyrex glass, silica glass, or any one of these glass coated with a transparent conductive film, or a transparent electrode substrate used in solid state image pick up devices. A black matrix is formed on the substrate to separate each color pixel element.
The developer solution is preferably an alkali aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium silicate, sodium methylsilicate, aqueous ammonia, ethylamine, diethylamine, dimethyl ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diaza-bicyclo(5,4,0)-7-undecene, or the like. The concentration of the developer in the solution is from 0.001 wt % to 10 wt %, preferably from 0.005 wt % to 5 wt %, and more preferably from 0.01 wt % to 1 wt %.
The backlight unit 20 is coupled to the second substrate 14 of the liquid crystal display element 10, and emits a light having a color temperature ranging from 6,000 K to 20,000 K. The useful examples of the backlight unit 20 include, but are not limited to, a white light emitting diode, a trichrome fluorescent lamp, or a combination thereof.
In the light-emitting mechanism for the white light emitting diode used as the backlight unit 20, blue light emitted from a light-emitting layer of a light-emitting die is absorbed by photoluminescent phosphor and is then transferred into a light of other color. Some energy is lost during the transfer. When the color temperature of the backlight unit 20 is lower than 6,000 K, the amount of the photoluminescent phosphor should be increased. The extent of the energy lost due to the transfer is increased, which results in decrease of the luminescent intensity. Therefore, it is difficult to enhance the luminance of the display in the bright state, and the contrast is reduced. On the other hand, when the color temperature of the backlight unit 20 is higher than 20,000 K, the amount of the photoluminescent phosphor should be decreased. The luminescent intensity of the red light is reduced and the brightness of the red light is too low.
In the case that the trichrome fluorescent lamp is used as the backlight unit 20, when the color temperature of the backlight unit 20 is lower than 6,000 K, the amount of red phosphor should be increased. The luminescent intensity of red light is too high, which results in light leakage in the dark state. Therefore, the contrast is reduced. On the other hand, when the color temperature of the backlight unit 20 is higher than 20,000 K, the amount of the red phosphor should be decreased. The luminescent intensity of the red light is reduced, and the brightness of the red light is too low.
Therefore, as described above, the range of the color temperature of the backlight unit 20 in the present invention is from 6,000 K to 20,000 K, preferably from 6,500 K to 19,000 K, and more preferably from 7,000 K to 18,000 K.
When the white light emitting diode is used as the backlight unit 20, a light-emitting layer of a blue light emitting die is formed with a fluorescence filter film containing the photoluminescent phosphor on the surface thereof, or a package material of the blue light emitting die contains the photoluminescent phosphor. The light emitting layer of the blue light emitting die is made of a nitride compound semiconductor, a group III-V compound semiconductor, a group II-IV compound semiconductor, a group IV-VI compound semiconductor, or combinations thereof, and has a main peak of luminescent spectrum ranging from 430 nm to 500 nm. Preferably, the light emitting layer of the blue light emitting die is made of InGaN or GaN material in combination with yellow phosphor and/or green phosphor and/or red phosphor so as to obtain the backlight unit 20 having the aforesaid desirable range of the color temperature.
Specifically, the photoluminescent phosphor includes at least one yellow or green phosphor selected from a cerium activated aluminum garnet phosphor, an alkaline earth metal silicate phosphor, or a combination thereof. When the photoluminescent phosphor is the yellow phosphor, the cerium activated aluminum garnet phosphor is a phosphor of RE3(Al,Ga)5O12:Ce, a phosphor of (Tb,Al)5O12:Ce, or a combination thereof, wherein RE is Y, Gd, La, or combinations thereof. The alkaline earth metal silicate phosphor is a phosphor of AE2SiO4:Eu, a phosphor of Sr3SiO5:Eu2+, or a combination thereof, wherein AE is Sr, Ba, Ca, or combinations thereof. When the photoluminescent phosphor is the green phosphor, the cerium activated aluminum garnet phosphor is a phosphor of RE3 (Al,Ga)5O12:Ce, wherein RE is Y, Gd, La, or combinations thereof. The alkaline earth metal silicate phosphor is a phosphor of AE2SiO4:Eu, a phosphor of Ca3Sc2Si3O12:Ce, or a combination thereof, wherein AE is Sr, Ba, Ca, or combinations thereof. Additionally, when the photoluminescent phosphor is the green phosphor, Ca3Sc2O4:Ce can also be used as the green phosphor.
Preferably, the photoluminescent phosphor can further include a red phosphor of a europium activated phosphor, a europium activated sulfide phosphor, a europium activated nitride phosphor, or combinations thereof. The europium activated phosphor is Y2O3:Eu. The europium activated sulfide phosphor is Y2O2S:Eu, La2O2S:Eu, or a combination thereof. The europium activated nitride phosphor is AE2Si5N8:Eu2+, CaAlSiN3:Eu2+, CaAlSiBN3:Eu, or combinations thereof, wherein AE is Sr, Ba, Ca, or combinations thereof.
Specifically referring to FIG. 2, in the manufacturing of the white light emitting diode, a light-emitting die 21 and a substrate 22 are prepared. The light-emitting die 21 emits light having a primary wavelength of 460 nm. The substrate 22 has a recessed holding member 221 defining a receiving space 23. The recessed holding member 221 has a bottom portion electrically connected to an external power source. The light-emitting die 21 is mounted on and electrically connects to the bottom portion of the recessed holding member 221. Polysiloxane resin containing the photoluminescent phosphor 241 is filled into the receiving space 23 until that the polysiloxane resin is flush with the substrate 22. The polysiloxane resin is cured at 70° C. for 3 hours and then at 150° C. for 1 hour so as to form a package layer 24 containing the photoluminescent phosphor 241.
When the trichrome fluorescent lamp is used as the backlight unit 20, the trichrome fluorescent lamp includes a phosphor combination including a blue phosphor, a green phosphor, and a red phosphor. If the amount of the blue phosphor is increased, the light emitted by the trichrome fluorescent lamp is bluish white, and the color temperature of the backlight unit 20 is increased. If the amount of the red phosphor is increased, the light emitted by the trichrome fluorescent lamp is reddish white, and the color temperature of the backlight unit 20 is decreased. In view of the color temperature, the blue phosphor is selected from Sr5(PO4)3Cl:Eu, (SrCaBa)5(PO4)3Cl:Eu, BaMg2Al16O27:Eu, and combinations thereof, the green phosphor is selected from LaPO4:Ce, LaPO4:Tb, LaPO4:CeTb, (CeTb)MgAl14O19, and combinations thereof, and the red phosphor is Y2O3:Eu. Preferably, the blue phosphor is in an amount ranging from 20 to 55 wt %, the green phosphor is in an amount ranging from 20 to 55 wt %, and the red phosphor is in an amount ranging from 20 to 45 wt % based on a total weight of the phosphor combination.
Color Liquid Crystal Display:
Referring once again to FIG. 1, as described above, the color liquid crystal display device of the present invention includes the liquid crystal display element 10 and the backlight unit 20.
The liquid crystal display element 10 includes the first substrate 13, the second substrate 14 spaced apart from the first substrate 13, the color filter 11 coupled to the first substrate 13, two alignment layers 15 respectively disposed on the color filter 11 and the second substrate 14 and facing toward each other, liquid crystal 12 disposed between the alignment layers 15, and two polarizers 16 respectively coupled to the first and second substrates 13, 14 and distal from the liquid crystal 12. The first substrate 13 is a color filter side substrate, and the second substrate 14 is a thin film transistor side substrate. The backlight unit 20 is coupled to the second substrate 14 so as to form the color liquid crystal display device.
The color liquid crystal display device of the present invention can be used with twisted nematic liquid crystal, super twisted nematic liquid crystal, in-plane switching liquid crystal, vertical alignment liquid crystal, optically compensated birefringence liquid crystal, ferroelectric liquid crystal, or the like.
EXAMPLES
The following examples are provided to illustrate the preferred embodiments of the invention, and should not be construed as limiting the scope of the invention.
Synthesis of Alkali-Soluble Resin
Synthesis Example B-1
A 1000 ml four-necked conical flask equipped with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer was purged with nitrogen, and was added continuously with 45 parts by weight of 2-methacryloylethoxy succinate monoester (referred to as HOMS hereinafter), 15 parts by weight of styrene monomer (referred to as SM hereinafter), 10 parts by weight of dicyclopentenyloxyethyl acrylate (referred to as DCPOA hereinafter), 25 parts by weight of benzyl methacrylate (referred to as BzMA hereinafter), 5 parts by weight of methyl acrylate (referred to as MA hereinafter), and 200 parts by weight of ethyl 3-ethoxypropionate (referred to as EEP hereinafter, as a solvent).
The contents in the four-necked conical flask were stirred while the temperature of an oil bath was raised to 100° C. 4 parts by weight of 2,2′-azobis-2-methyl butyronitrile (referred to as AMBN hereinafter, as a polymerization initiator) dissolved in EEP was added into the four-necked conical flask in five aliquots within one hour.
Polymerization was conducted at 100° C. for 6 hours. Polymerization product was removed from the four-necked conical flask after the polymerization was complete. The solvent was evaporated so as to obtain an alkali-soluble resin (B-1).
Synthesis Examples B-2 and B-3
Synthesis Examples B-2 and B-3 were conducted in a manner identical to that of Synthesis Example 1 using the components, the amounts thereof, and the reaction conditions shown in Table 1.







TABLE 1







Synthesis Examples of alkali-soluble resin:












Composition (parts by weight)

Reaction
Reaction













Syn.
Monomers for Polymerization
Initiator
Solvent
Feeding
Temp.
Time



















Ex.#
HOMS
MAA
SM
DCPOA
BzMA
PMI
MA
AMBN
EEP
manner
(° C.)
(hrs)






















B-1
45

15
10
25

5
4
200
Continuously
100
6


B-2

35
10

35
5
10
4
200
Continuously
100
6


B-3
25
20
5
10
30

5
4
200
Continuously
100
6





Note:


HOMS: 2-methacryloyloxyethyl succinate monoester


MAA: methacrylic acid


SM: styrene monomer


DCPOA: dicyclopentenyloxyethyl acrylate


BzMA: benzyl methacrylate


PMI: N-phenylmaleimide


MA: methyl acrylate


AMBN: 2,2′-azobis-2-methyl butyronitrile


EEP: ethyl 3-ethoxypropionate






Preparation Examples of Red Photosensitive Resin Composition
Preparation Example a
160 parts by weight of C.I. Pigment Red 242, 20 parts by weight of C.I. Pigment Red 89, 20 parts by weight of C.I. Pigment Yellow 150, 90 parts by weight of the alkali-soluble resin (B-1) obtained from Synthesis Example B-1, 10 parts by weight of the alkali-soluble resin (B-3) obtained from Synthesis Example B-3, 90 parts by weight of dipentaerythritol hexaacrylate (referred to as C-1 hereinafter, manufactured by Toagosei), 10 parts by weight of TO-1382 (referred to as C-2 hereinafter, manufactured by Toagosei), 10 parts by weight of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethylketo 1-(O-acetyloxime) (referred to as D-1 hereinafter), parts by weight of 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole (referred to as D-2 hereinafter), 4 parts by weight of 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine (referred to as D-3 hereinafter), and 2,100 parts by weight of ethyl 3-ethoxypropionate (referred to as E-1 hereinafter, used as a solvent) were mixed using a shaker to obtain a red photosensitive resin composition.
Preparation Examples b to n
Preparation Examples b to n were conducted in a manner identical to that of Preparation Example a using the components and the amounts thereof shown in Table 2.







TABLE 2







Preparation Examples a to n:









Preparation Examples





















Components
a
b
c
d
e
f
g
h
i
j
k
l
m
n


























Pigments
A-1
C.I.

140



60

180








pbw

Pigment




Red 166




C.I.
160

120
100
80

40

20

200
100
100




Pigment




Red 242



A-2
C.I.
40

80
100
120

160
20
180
200




Pigment




Red 89




C.I.

60



140




Pigment




Red 177



A-3
C.I.











100
100
165




Pigment




Red 254



A-4
C.I.

15



20

20

20



85




Pigment




Yellow




139




C.I.
20

10

10

15

20

20

10




Pigment




Yellow




150





















Weight ratio (A-1)/(A-2)
80/20
70/30
60/40
50/50
40/60
30/70
20/80
90/10
10/90
0/100
100/0
100/0
100/0























Alkali-soluble
B-1
90

90

90

90
90

90

90

90


resin
B-2

90

90

90


90

90

90



B-3
10
10
10
10
10
10
10
10
10
10
10
10
10
10


A compound
C-1
90
80
100
50
90
80
90
90
90
90
90
80
80
90


having an
C-2
10
20

50
10
20
10
10
10
10
10
20
20
10


ethylenic group


Photoinitiator
D-1
10
10
10
10
10
10
10
10
10
10
10
10
10
10



D-2
4
4
4
4
4

4
4
4
4
4
4
4
4



D-3
4
4
4
4
4
4

4
4
4
4
4
4
4


Solvent
E-1
2100
2200


1100
1000
900


1100
1100
2100
2200



E-2


2100
2200
1000
1100
1300
2100
2200
1000
1000


2100





Note:


C-1: pentaerythritol triacrylate (manufactured by Toagosei)


C-2: TO-1382 (manufactured by Toagosei)


D-1: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethylketo 1-(O-acetyloxime)


D-2: 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole


D-3: 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine


E-1: ethyl 3-ethoxypropionate


E-2: propylene glycol methyl ether acetate






Preparation Example of Green Photosensitive Resin Composition
A green photosensitive resin composition was prepared in a manner identical to that of Preparation Example a except the following were used: 150 parts by weight of C.I. Pigment Green 58, 100 parts by weight of C.I. Pigment Yellow 150, 90 parts by weight of the alkali-soluble resin (B-1) obtained from Synthesis Example B-1, 10 parts by weight of the alkali-soluble resin (B-3) obtained from Synthesis Example B-3, 90 parts by weight of the ethylenic compound (C-1), 10 parts by weight of the ethylenic compound (C-2), 8 parts by weight of the photoinitiator (D-1), 8 parts by weight of the photoinitiator (D-2), 4 parts by weight of the photoinitiator (D-3), and 2,100 parts by weight of the solvent (E-1).
Preparation Example of Blue Photosensitive Resin Composition
A blue photosensitive resin composition was prepared in a manner identical to that of Preparation Example a except the following were used: 240 parts by weight of C.I. Pigment Blue 15:6, 10 parts by weight of C.I. Pigment Purple 23, 90 parts by weight of the alkali-soluble resin (B-1) obtained from Synthesis Example B-1, 10 parts by weight of the alkali-soluble resin (B-3) obtained from Synthesis Example B-3, 90 parts by weight of the ethylenic compound (C-1), 10 parts by weight of the ethylenic compound (C-2), 10 parts by weight of the photoinitiator (D-1), 5 parts by weight of the photoinitiator (D-3), 5 parts by weight of 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and 2, 100 parts by weight of the solvent (E-1).
Preparation of a Color Filter
Preparation Example 11-a
The red photosensitive resin composition obtained in Preparation Example a was spin-coated on a glass substrate, dried under a pressure of 100 mm Hg for 30 seconds, and was pre-baked at a temperature of 80° C. for 3 minutes to form a pre-baked film having a thickness of 2.5 μm. The pre-baked film was exposed using a mask aligner (Canon PLA-501F, 300 mJ/cm2), was immersed into a developer solution at a temperature of 23° C. for 2 minutes, was washed with water, and was post-baked at a temperature of 200° C. for 80 minutes to form a red pixel pattern. The aforesaid procedure was repeated to form a green pixel pattern and a blue pixel pattern. A pixel layer having a thickness of about 2.0 μm was obtained thereby.
An ITO (indium tin oxide) film was deposited on the pixel layer at a temperature of 235° C. under vacuum. The ITO film can be etched and formed with a wiring layout, if necessary. A color filter was obtained thereby.
Preparation Examples 11-b to 11-n
Preparation Examples 11-b to 11-n were conducted in a manner identical to that of Preparation Example 11-a using the red photosensitive resin compositions obtained in Preparation Examples b to n.
Preparation of a Liquid Crystal Display Element
Polyimide was applied on an ITO layer deposited on each of the substrate formed with the color filter and a substrate formed with a thin film transistor and was heated to form an alignment layer. The two substrates were arranged to oppose each other with a spacer (cell gap). The peripheral portions of the two substrates were joined together with a sealing agent, liquid crystals were filled into the cell gap defined by the surfaces of the substrates and the sealing agent, and an injection hole was sealed up to form a liquid crystal cell. Then, a polarizer was affixed to the exterior sides of the liquid crystal cell to obtain the liquid crystal display element.
Preparation of a Backlight Unit
Preparation Examples 20-1-1 to 20-1-6
A blue light-emitting die of InGaN (manufactured by Chi Mei Lighting Technology Corp., light-emitting wavelength of 460 nm) was mounted on a recessed holding member and was electrically connected to a bottom portion of the recessed holding member. Polysiloxane resin containing yellow phosphor and red phosphor in a blending ratio shown in Table 3 was filled into a receiving space defined by the recessed holding member until the polysiloxane resin was flush with the recessed holding member. The polysiloxane resin was cured to obtain a white light emitting diode used as the backlight unit.







TABLE 3







Preparation Examples of a white light


emitting diode used as a backlight unit

















Color


Prep.




temp.


Ex. #
Yellow phosphor
Pbw
Red phosphor
pbw
(K)















20-1-1
(SrBa)2SiO4:Eu
18
CaAlSiBN3:Eu
2.5
3934


20-1-2
(SrBa)2SiO4:Eu
17
CaAlSiBN3:Eu
2
6050


20-1-3
Y3(Al,Ga)5O12:Ce
15
CaAlSiBN3:Eu
2
11377


20-1-4
Y3(Al,Ga)5O12:Ce
14
CaAlSiBN3:Eu
1
15350


20-1-5
Y3(Al,Ga)5O12:Ce
13.2
Y2O3:Eu
0.9
19805


20-1-6
Y3(Al,Ga)5O12:Ce
11
Y2O3:Eu
0.5
22260





Note:


1. pbw: parts by weight


2. light-emitting wavelength of (SrBa)2SiO4:Eu: 550-570 nm


3. light-emitting wavelength of Y3(Al,Ga)5O12:Ce: 520-550 nm


4. light-emitting wavelength of CaAlSiBN3:Eu: 650-670 nm


5. light-emitting wavelength of Y2O3:Eu: 610-630 nm






Measurement of Color Temperature of a Backlight Unit:

CIE chromaticity coordinate value and brightness of a backlight unit were determined using a colorimeter (manufactured by Otsuka Electronics Co., Model No. MCPD). Color temperature of the backlight unit could be determined from the chromaticity coordinate value and isotemperature line.
Preparation Examples 20-2-1 to 20-2-6
Red phosphor of Y2O3:Eu, green phosphor of LaPO4:Ce, Tb, and blue phosphor of (SrCaBa)5(PO4)3Cl:Eu were blended together in a blending ratio shown in Table 4 to obtain a phosphor blend, which was mixed with a butyl acetate solution of nitrocellulose to obtain a suspension. The suspension was applied to an inner surface of a glass tube having an inner diameter of 32 mm and was dried to form a coating layer on the inner surface of the glass tube. The coating layer was baked at a temperature of 500° C. to form a trichrome fluorescent lamp of 40 W used as the backlight unit. The color temperature of each of the trichrome fluorescent lamps obtained in Preparation Examples 20-2-1 to 20-2-6 were also shown in Table 4.







TABLE 4







Preparation examples of a trichrome fluorescent


lamp used as the backlight unit










Blending ratio
Color











Prep.
Red phosphor
Green phosphor
Blue phosphor
temp.


Ex. #
(%)
(%)
(%)
(K)














20-2-1
40
35
25
3512


20-2-2
35
35
30
6105


20-2-3
34
33
33
10894


20-2-4
32
33
35
15536


20-2-5
31
32
37
19780


20-2-6
30
30
40
22122





Red phosphor: Y2O3:Eu


Green phosphor: LaPO4:Ce,Tb


Blue phosphor: (SrCaBa)5(PO4)3Cl:Eu






Examples of Color Liquid Crystal Display Device
Example 1
The liquid crystal display element made from the color filter obtained in Preparation Example 11-a was coupled to the backlight unit obtained in Preparation Example 20-1-2 to obtain a color liquid display device, which was evaluated according to the following evaluation methods. The evaluation results are shown in Table 5-1.
Contrast Measurement:
Luminance of red light displayed by a color liquid crystal display device at a bright state and at a dark state were measured using a luminance meter (manufactured by Topcon, Japan, Model No. BM-5A). The value of contrast (Rc) can be obtained from a ratio of the luminance at the bright state to the luminance at the dark state.
⊚: Rc≧2000
◯: 1500≦Rc<2000
Δ: 1000≦Rc<1500
X: Rc<1000
CIE chromaticity coordinate value (x,y) and brightness (Y) of a color liquid crystal display were determined using a colorimeter (manufactured by Otsuka Electronics Co., Model No. MCPD). The brightness (Y) of red color displayed by the color liquid crystal display was used for the brightness evaluation.
⊚: Y≧20
◯: 15≦Y<20
Δ: 10≦Y<15
X: Y<5
Examples 2 to 8
Examples 2 to 8 were conducted in a manner identical to that of Example 1 using the color filters and the backlight units shown in Table 5-1. The evaluation results of Examples 2 to 8 are also shown in Table 5-1.
Comparative Examples 1 to 11
Comparative Examples 1 to 11 were conducted in a manner identical to that of Example 1 using the color filters and the backlight units shown in Table 5-2. The evaluation results of Comparative Examples 1 to 11 are also shown in Table 5-2.









TABLE 5-1









Examples















Components
1
2
3
4
5
6
7
8





Color filter
11-a
11-b
11-c
11-d
11-d
11-e
11-f
11-g


Weight ratio of
80/20
70/30
60/40
50/50
50/50
40/60
30/70
20/80


(A-1)/(A-2)


Backlight unit
20-2-2
20-2-3
20-2-4
20-2-5
20-1-2
20-1-3
20-1-4
20-1-5


Color temp. of
6105
10894
15536
19780
6050
11377
15350
19805


backlight unit
















results
Contrast
⊚
⊚
⊚
⊚
⊚
⊚
⊚
◯



Brightness
◯
⊚
⊚
⊚
⊚
⊚
⊚
⊚


















TABLE 5-2









Comparative examples


















Components
1
2
3
4
5
6
7
8
9
10
11





Color filter
11-b
11-h
11-j
11-l
11-n
11-d
11-c
11-i
11-k
11-m
11-e


Weight ratio
70/30
90/10
0/100
100/0
—
50/50
60/40
10/90
100/0
100/0
40/60


of (A-1)/(A-2)


Backlight unit
20-2-1
20-2-2
20-2-3
20-2-4
20-2-5
20-2-6
20-1-1
20-1-2
20-1-3
20-1-4
20-1-6


Color temp. of
3512
6105
10894
15536
19780
22122
3934
6050
11377
15350
22260


backlight unit



















results
Contrast
Δ
Δ
X
X
X
X
Δ
X
X
X
X



brightness
X
X
X
X
X
Δ
X
Δ
X
X
Δ









As shown in Table 5-1, a color liquid crystal display device having high brightness and high contrast can be obtained when a weight ratio of (A-1) an azo-based red pigment to (A-2) an anthraquinone-based red pigment is controlled to be within a range from 20/80 to 80/20 and a color temperature of a backlight unit is controlled to be within a range from 6,000 K to 20,000 K.
While the present invention has been described in connection with what are considered the most practical and preferred embodiments, it is understood that this invention is not limited to the disclosed embodiments but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation and equivalent arrangements.

## Claims

1. A color liquid crystal display device, comprising:
a liquid crystal display element including a color filter having a red filter segment, a green filter segment, and a blue filter segment, said red filter segment being prepared from a red photosensitive resin composition which includes a pigment combination, an alkali-soluble resin, a compound having an ethylenic group, and a photoinitiator, said pigment combination including an azo-based red pigment and an anthraquinone-based red pigment, a weight ratio of said azo-based red pigment to said anthraquinone-based red pigment ranging from 20/80 to 80/20; and
a backlight unit coupled to said liquid crystal display element and having a color temperature ranging from 6,000 K to 20,000 K.

2. The color liquid crystal display device as claimed in claim 1, wherein said weight ratio of said azo-based red pigment to said anthraquinone-based red pigment ranges from 30/70 to 80/20.

3. The color liquid crystal display device as claimed in claim 1, wherein said azo-based red pigment is selected from a group consisting of C.I. Pigment Red 144, C.I. Pigment Red 166, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 242, C.I. Pigment Red 248, C.I. Pigment Red 262, and combinations thereof.

4. The color liquid crystal display device as claimed in claim 1, wherein said anthraquinone-based red pigment is selected from a group consisting of C.I. Pigment Red 83, C.I. Pigment Red 89, P.I. Pigment Red 177, and combinations thereof.

5. The color liquid crystal display device as claimed in claim 1, wherein said pigment combination further includes a yellow pigment selected from a group consisting of an isoindole-based yellow pigment, a quinaphthalone-based yellow pigment, an anthraquinone-based yellow pigment, and combinations thereof.

6. The color liquid crystal display device as claimed in claim 5, wherein said yellow pigment is said quinaphthalone-based yellow pigment.

7. The color liquid crystal display device as claimed in claim 6, wherein said quinaphthalone-based yellow pigment is C.I. Pigment Yellow 150.

8. The color liquid crystal display device as claimed in claim 1, wherein said backlight unit is selected from a group consisting of a white light emitting diode, a trichrome fluorescent lamp, and a combination thereof.

9. The color liquid crystal display device as claimed in claim 8, wherein said backlight unit is said white light emitting diode including a light emitting layer having a main peak of luminescent spectrum ranging from 430 nm to 500 nm, and a photoluminescent phosphor, said light emitting layer being made of a material selected from a group consisting of a nitride compound semiconductor, a group III-V compound semiconductor, a group II-IV compound semiconductor, a group IV-VI compound semiconductor, and combinations thereof.

10. The color liquid crystal display device as claimed in claim 9, wherein said photoluminescent phosphor includes a yellow or green phosphor selected from a group consisting of a cerium activated aluminum garnet phosphor, an alkaline earth metal silicate phosphor, and a combination thereof.

11. The color liquid crystal display device as claimed in claim 10, wherein said photoluminescent phosphor is a yellow phosphor, said cerium activated aluminum garnet phosphor being selected from a group consisting a phosphor of RE3(Al,Ga)5O12:Ce, a phosphor of (Tb,Al)5O12:Ce, and a combination thereof, wherein RE is selected from a group consisting of Y, Gd, La, and combinations thereof, said alkaline earth metal silicate phosphor being selected from a group consisting of a phosphor of AE2SiO4:Eu, a phosphor of Sr3SiO5:Eu2+, and a combination thereof, wherein AE is selected from a group consisting of Sr, Ba, Ca, and combinations thereof.

12. The color liquid crystal display device as claimed in claim 10, wherein said photoluminescent phosphor is a green phosphor, said cerium activated aluminum garnet phosphor being a phosphor of RE3(Al,Ga)5O12:Ce, wherein RE is selected from a group consisting of Y, Gd, La, and combinations thereof, said alkaline earth metal silicate phosphor being selected from a group consisting of a phosphor of AE2SiO4:Eu, a phosphor of Ca3Sc2Si3O12:Ce, and a combination thereof, wherein AE is selected from a group consisting of Sr, Ba, Ca, and combinations thereof.

13. The color liquid crystal display device as claimed in claim 9, wherein said photoluminescent phosphor includes a green phosphor selected from a group consisting of RE3 (Al,Ga)5O12:Ce, AE2SiO4:Eu, Ca3Sc2Si3O12:Ce, Ca3Sc2O4:Ce, and combinations thereof, wherein RE is selected from a group consisting of Y, Gd, La, and combinations thereof, and wherein AE is selected from a group consisting of Sr, Ba, Ca, and combinations thereof.

14. The color liquid crystal display device as claimed in claim 10, wherein said photoluminescent phosphor further includes a red phosphor selected from a group consisting of a europium activated phosphor, a europium activated sulfide phosphor, a europium activated nitride phosphor, and combinations thereof.

15. The color liquid crystal display device as claimed in claim 14, wherein said europium activated phosphor is Y2O3:Eu, said europium activated sulfide phosphor being selected from a group consisting of Y2O2S:Eu, La2O2S:Eu, and combinations thereof, said europium activated nitride phosphor being selected from a group consisting of AE2Si5N8:Eu2+, CaAlSiN3:Eu2+, CaAlSiBN3:Eu, and combinations thereof, wherein AE is selected from a group consisting of Sr, Ba, Ca, and combinations thereof.

16. The color liquid crystal display device as claimed in claim 8, wherein said backlight unit is said trichrome fluorescent lamp which includes a phosphor combination including a blue phosphor, a green phosphor, and a red phosphor.

17. The color liquid crystal display device as claimed in claim 16, wherein said blue phosphor is selected from a group consisting of Sr5(PO4)3Cl:Eu, (SrCaBa)5(PO4)3Cl:Eu, BaMg2Al16O27:Eu, and combinations thereof, said green phosphor is selected from a group consisting of LaPO4:Ce, LaPO4:Tb, LaPO4:CeTb, (CeTb)MgAl14O19, and combinations thereof, and said red phosphor is Y2O3:Eu.

18. The color liquid crystal display device as claimed in claim 16, wherein said blue phosphor is in an amount ranging from 20 to 55 wt %, said green phosphor is in an amount ranging from 20 to 55 wt %, and said red phosphor is in an amount ranging from 20 to 45 wt % based on a total weight of said phosphor combination.